Methods of combatting nematodes using phosphono thioester amidates

ABSTRACT

COMPOUNDS HAVING THE FORMULA   R1-S-P(=X)(-R6)-R3   WHERE R1 IS TRICHLOROETHYL OR DICHLOROVINYL, R2 IS LOWER ALKYL OR PHENYL, R3 IS   -O-R4, OR -S-R4, OR -N(-R5)-R6   WHERE R4 IS ALKYL, HALOALKYL OR HALOARYL, R5 IS ALKYL, ARYL OR HALOARYL AND X IS O OR S. PREFERABLY R4 AND R5 ARE LOWER ALKYL AND R6 IS H OR LOWER ALKYL ARE USEFUL AS NEMATOCIDES, FUNGICIDES, AND INSECTICIDES. PREFERABLY R1 IS 2,2,2-TRICHLOROETHYL OR 2,2-DICHLOROVINYL.

nited States Patent Int. Cl. A01n 9/36 US. Cl. 424-219 7 Claims ABSTRACTOF THE DISCLOSURE Compounds having the formula II RiS ll a e where R istrichloroethyl or dichlorovinyl, R is lower alkyl or phenyl, R is OR; orS R4 or N where R, is alkyl, aryl, haloalkyl or haloaryl, R is alkyl,aryl or haloaryl and X is O or S. Preferably R and R are lower alkyl andR is H or lower alkyl are useful as nematocides, fungicides, andinsecticides. Preferably R is 2,2,2-trichloroethyl or 2,2-dichlorovinyl.

This is a division of application Ser. No. 196,183, filed Nov. 5, 1971.Application 'Ser. No. 196,183 is a division of application Ser. No.889,688 filed Dec. 31, 1969 and the present application also is adivision of application Ser. No. 889,688, which is acontinuation-in-part of application Ser. No. 620,664, filed Mar. 6,1967, and now Pat. No. 3,489,825, Jan. 13, 1970. The entire disclosureof the parent application is hereby incorporated by reference.Application 196,183 is now Pat. 3,702,890 and application 889,688 is nowPat. 3,666,842.

The present invention relates to the preparation of novel phosphonates,thiophosphonates, phosphonamidates and thiophosphonamidates.

It is an object of the present invention to prepare novel phosphonates,thiophosphonates, phosphonamidates and thiophosphonamidates.

Another object is to kill nematodes.

An additional object is to kill fungi.

A further object is to kill insects.

Still further objects and the entire scope of applicability of thepresent'invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of. the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be attained by preparingcompounds having the formula Patented Oct. 30, 1973 where R istrichloroethyl or dichlorovinyl, R is lower alkyl or phenyl, R is s 0 R4or SR4 or N where R, is alkyl, aryl, haloalkyl or haloaryl, R is alkyl,aryl or haloaryl and R is hydrogen or R and X is O or S. Preferably Rand R are lower alkyl, e.g. 1-8 carbon atoms and most preferably notover 4 carbon atoms, and R is H or lower alkyl (as for R and R If ahalogen is present on R R or R it is preferably chlorine but can bebromine or fluorine. Preferably R is 2,2,2- trichloroethyl or2,2-dichlorovinyl.

The compounds of the invention are useful as nematocides, fungicides andinsecticides. The activity of the compounds for the several uses variesto a considerable extent depending upon both the compound and itsintended use. Because of their relatively low phytotoxicity, they arevery useful as agricultural pesticides.

The compounds of the present invention are conveniently prepared by thefollowing reaction:

I II III The compounds of Formula I include S-2,2,2-trichloroethylmethyl phosphonyl chloride (CP 12), SF2,2,2-trichloroethyl ethylphosphonyl chloride (CP 22), S,2,2,2- trichloroethyl propyl phosphonylchloride, S-2,2,2-trichloroethyl butyl phosphonyl chloride,S-2,2,2-trichloroethyl isobutyl phosphonyl chloride,S-l,2,2,-trichloroethyl methyl phosphonyl chloride,S-1,2,2-trichloroethyl ethyl phosphonyl chloride, S-2,2,2-trichloroethylphenyl phosphonyl chloride (CP 8), S-1,2,2,-trichloroethyl phenylphosphonyl chloride, S-2,2-dichlorovinyl methyl phosphonyl chloride (CP14), S-2,2-dichlorovinyl ethyl phosphonyl chloride (CP 23),S-2,2-dichlorovinyl propyl phosphonyl chloride, S-2,2-dichlorovinylisopropyl phosphonyl chloride, S-2,2-dichlorovinyl butyl phosphonylchloride, S-2,2-dichlorovinyl phenyl phosphonyl chloride (CP 10),S-2,2,2-trichloroethyl methyl thiophosphonyl chloride (CP 16),S-2,2,2-trichloroethyl ethyl thiophosphonyl chloride (CP 32),S-2,2,2,-trichloroethyl propyl thio and phosphonyl chloride,S-2,2,2-trichloroethyl butyl thiophosphonyl chloride,S-2,2,2-trichloroethy1 phenyl thiophosphonyl chloride (CP 9),S-1,2,2-trichloroethyl methyl thiophosphonyl chloride,S-1,2,2-trichloroethyl ethyl thiophosphonyl chloride,S-1,2,2-trichloroethyl thiophosphonyl chloride, S-2,2-dichlorovinylmethyl thiophosphonyl chloride (CP 15), S-2,2-dichlorovinyl ethylthiophosphonyl chloride (CP 33), S-2,2-dichlorovinyl propylthiophosphonyl chloride, S-2,2-dichlorovinyl butyl thiophosphonylchloride, S-2,2-dichlorovinyl phenyl thiophosphonyl chloride (CP 11).

As compounds of Formula II for reaction with compounds of Formula Ithere can be used alcohols such as methyl alcohol, ethyl alcohol, propylalcohol, isopropyl alcohol, butyl alcohol, octyl alcohol, sec. octylalcohol, isooctyl alcohol, amyl alcohol, 2,2,2-trichloroethyl alcohol,ethylene chlorohydrin, propylene chlorohydrin, trimethylenechlorohydrin, 1,2-dichloro-2-propanol, ethylene bromohydrin, allylalcohol, or phenols (preferably in the form of their sodium salts), e.g.phenol per se, pcresol, m-cresol, 'o-cresol, p-ethyl phenol,2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, p-t-butyl phenol,poctylphenol, 2 methyl-4-chlorophenol, 2,4,5 trichlorophenol,p-butylphenol, or mercaptans, e.g. methyl mercaptan, isopropylmercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, sec.butyl mercaptan, thiophenol,

p-t-butyl thiophenol, amyl mercaptan, octyl mercaptan,2,4,5-trichlorothiophenol, 2-methyl-4-chlorothiophenol; or primary orsecondary amines, e.g. methyl amine, ethyl amine, isopropyl amine,propyl amine, butyl amine, isobutyl amine, amyl amine, hexyl amine,cyclohexyl amine, piperidine, pyrrolidine, octyl amine, dimethyl amine,diethyl amine, dipropyl amine, dibutyl amine, diamyl amine, diisopropylamine, aziridine (ethylene imine), dioctyl amine, diisobutyl amine,aniline, N-methylaniline, N-ethyl aniline, m-chloro aniline, a-naphthylamine, B-naphthyl amine, p-bromoaniline, N-butyl aniline, o-toluidine,ptoluidine, p-chloroaniline, -O-chloroaniline.

Examples of compounds within the present invention areS2,2,2-trichloroethyl O-butyl methyl phosphonate,S-2,2,2-trichloroethyl-O-butyl thiophosphonate, S-2,2,2- trichloroethylO-amyl ethyl phosphonate, S-2,2,2-trichlo roethyl-O-amylthiophosphonate, S-2,2,2-trichloroethyl O-octyl methyl phosphonate,S-2,2,2-trichloroethyl O-octyl ethyl thiophosphonate,S-2,2,2-trichloroethyl O-butyl butyl phosphonate, S-2,2,2-trichloroethylO-hexyl butyl thiophosphonate, S,S-dichlorovinyl O-butyl methylphosphonate, S,S-dichlorovinyl O octyl ethyl thiophosphonate,S-1,2,2-trichloroethyl O-ethyl methyl phosphonate, S-1,2,2-trichloroethyl O-methyl eth'yl thiophosphonate, S-2,2,2-trichloroethyl O-2-chloroethyl methyl thioposphonate,S-2,2,2-trichloroethyl O-2-bromoethyl ethyl ethyl phosphonate,S-2,2,2-trichloroethyl-O-phenyl methyl phosphonate,S-2,2,2-trichloroethyl-O-phenyl ethyl thiophosphonate,S-2,2-dichlorovinyl-O-phenyl ethyl phosphonate,S-2,2-dichlorovinyl-O-phenyl methyl thiophosphonate,S-2,2-dichlorovinyl-O-phenyl phenyl phosphonate, S-2, 2,2-trichloroethylO p cresyl methyl phosphonate, S-2,2,2-trichloroethyl O-m-cresyl ethylthiophosphonate, S-2,2-dichlorovinyl O-o-cresyl ethyl thiophosphonate,S-2,2,2-trichloroethyl-S-methyl methyl phosphonate, S-2, 2,2trichloroethyl S ethyl methyl thiophosphonate,S-2,2-dichlorovinyl-S-butyl ethyl phosphonate,S-2,2-dichlorovinyl-S-octyl methyl thiophosphonate,S-2,2,2-trichloroethyl-S-phenyl ethyl phosphonate,S-2,2,2-trichloroethyl methyl phosphon mono octyl amidate,S-2,2,2-trichloroethyl ethyl phosphon dioctyl amidate, S-2,2-dichlorovinyl methyl phosphon mono butyl amidate, S-2,2,2-trichloroethylethyl thiophosphon diheptyl amidate, S-2,2-dichlorovinyl methylthiophosphon mono butyl amidate, S-2,2,2-trichloroethyl ethyl phosphonmonophenyl amidate, S-2,2-dichlorovinyl methyl phosphon mono alphanaphthyl amidate, S-2,2,2-trichloroethyl methyl thiophosphon diphenylamidate, S-2,2-dichlorovinyl ethyl phosphon p-chlorophenyl amidate.Additional compounds within the invention are set forth in the workingexamples.

In the working examples the compounds of Formula I are indicated by theappropriate CP numbers as set forth supra.

Unless otherwise indicated, all parts and percentages are by weight.

Specific examples of the preparation of such derivatives are set forthbelow.

EXAMPLE 1 6.1 grams (0.023 mole) of CP 12 were dissolved in 60 ml. ofSkellysolve B-benzene (1:5 by volume). 38 grams (0.023 mole) of2,4-dichlorophenol in 20 ml. of benzene were added and the reaction waseifected by dropwise addition of 2.3 grams (0.023 mole) of triethylaminein ml. of Skellysolve B with stirring and cooling at a temperature notto exceed 35 C. 1.5 hours Warming at 50 C., cooling, washing insuccession with dilute hydrochloric acid, dilute aqueous sodiumbicarbonate and water, drying over anhydrous magnesium sulfate and highvacuum stripping gave 8.8 grams (98% yield) of crudeS-2,2,2-trichloroethyl-O-2,4-dichlorophenyl methyl phosphonate (Compound6702) as a butt colored solid which after a short wash with SkellysolveB gave white 4 crystals, M.P. 86 C.; Cl, 44.7% (theory 45.6% S, 8.3%(theory, 8.25%); P, 7.9% (theory, 7.9%).

Skellysolve B is an aliphatic hydrocarbon solvent boiling in the hexanerange.

EXAMPLE 2 11.05 grams (0.04 mole) of CP 22 were diluted with 100 ml. ofdry chloroform and 4.2 grams (0.08 mole) of monoisopropyl amine in 10ml. of chloroform were added dropwise with stirring and cooling at 5l0C. After completed addition the whole mixture was allowed to stir atroom temperature overnight. Washing with dilute HCl, dilute NaI-ICO andwater, drying over anhydrous MgSO and stripping off of the chloroformgave 11.5 grams (96.5% yield) of S-2,2,2-trichloroethyl ethylphosphon-monoisopropyl amidate (Compound 7835) as a light amber viscousoil, 11 1.5213.

EXAMPLE 3 9.7 grams (0.03 mole) of CP 8 in 10 ml. of Skellysolve B wereadded to 3 grams (ie a large excess) of ethyl mercaptan in 50 ml. ofSkellysolve B. 3.0 grams of triethylamine (0.03 mole) in 10 ml. ofSkellysolve B were then added dropwise with stirring at below 35 C. overa period of 20 minutes. Stirring at room temperature for 2 furtherhours, washing the mixture with dilute HCl, dilute NaHCO and water,drying of the organic layer over MgSO and stripping gave 10.0 gramsyield) of S 2,2,2 trichloroethyl S ethyl phosphonate (Compound 6645) asan almost colorless and odorless viscous oil, 12 1.5992; Cl, 30.2%(theory, 30.5%); P, 8.7% (theory, 8.9%

EXAMPLE 4 11.1 grams (0.04 mole) of CP 16 were dissolved in ml. ofchloroform and 4.8 grams (0.08 mole) of monoisopropyl amine in 10 ml. ofchloroform were added dropwise with stirring at 5-10 C. with cooling.The mixture was allowed to warm to room temperature and stand overnight.Washing of the chloroform solution with dilute HCl, dilute NaHCO andwater, drying over anhydrous MgSO, and stripping of the organic solutiongave 11.5 grams (96% yield) of S-2,2,2-trichloroethyl methylthiophosphon-monoisopropyl amidate (Compound 7836) as an almostcolorless, very viscous oil, n 1.5747.

EXAMPLE 5 11.7 grams (0.04 mole) of CP 32 were dissolved in 100 ml. ofchloroform and a solution of 4.8 grams of monoisopropyl amine in 10 ml.of chloroform was added dropwise with stirring at 5-10 C. withoccasional cooling. Additional slow stirring overnight at roomtemperature, Washing of the resulting mixture in succession with diluteI-ICl, dilute NaHCO and water, drying over anhydrous magnesium sulfateand stripping gave a 90% yield of S- 2,2,2 trichloroethyl ethylthiophosphon monoisopropyl amidate as a viscous, colorles oil, n 1.5684(Compound EXAMPLE 6 10.2 grams of CP 9 (0.03 mole) were diluted with 50ml. of benzene and 2 grams (a slight excess) of ethyl alcohol wereadded. 3 grams (0.03 mole) of triethyl amine in 10 ml. of benzene wereadded with stirring and cooling at room temperature in order to completethe reaction. Standing overnight and Working up by washing with diluteHCl, dilute NaHCO- and water, drying over MgSO and high vacuum strippinggave 9.7 grams (93% yield) of S 2,2,2 trichloroethyl O ethyl phenylthiophosphonate (Compound 7823) as a yellow oil, n 1.6030.

EXAMPLE 7 13.55 grams (0.06 mole) of CP 14 dissolved in 100 ml. ofpetroleum ether were reacted with 7.2 grams (0.12 mole) of monoisopropylamine at room temperature. (The temperature did not exceed 30 C.) 50 ml.of benzene were added to make the product soluble in the organic layer.Washing with dilute HCl, dilute NaHCO and water, drying over MgSO andstripping gave 10 grams (67% yield) of S 2,2 dichlorovinyl methylphosphon monoisopropyl amidate (Compound 7587) as an amber, viscous oil,n 1.5486.

EXAMPLE 8 To 10 grams (0.052 mole) of CP 23 in 50 ml. of dry chloroformthere were added 3 grams (0.042 mole+0.5 gram excess) of ethyl mercaptanat -5 C. followed by dropwise addition of 4.25 grams (0.042 mole) oftriethylamine in 20 ml. of chloroform with cooling and stirring.Stirring at room temperature for 3 hours, washing with dilute HCl,dilute NaHCO and water and drying over MgSO gave after high vacuumstripping 9.9 grams (89% yield) of S 2,2 dichlorovinyl S ethyl ethylphosphonate (Compound 7502) as a light viscous oil, n 1.5756.

EXAMPLE 9 To 8.61 grams (0.03 mole) of CP 10 in 100 ml. of petroleumether stirred and cooled to 1015 C. there were added 3.0 grams (about a10% excess) of dimethylamine at a moderate rate at a temperature of notover 15' C. Finally the whole mixture was stirred for 30 minutes at roomtemperature. Addition of 50 m1. of benzene to dissolve all of theproduct formed, washing with dilute HCl, dilute NaHCO and water, dryingover MgSO and stripping of the organic layer gave 7.5 grams (85% yield)of S 2,2 dichlorovinyl phenyl phosphono N,N- dimethyl amidate (Compound6707) as a brown oil, n 1.5942.

EXAMPLE 10 To 9.5 grams (0.039 mole) of CP 15 in 100 ml. of chloroformthere were added with stirring and cooling at 1520 C. a solution of 4.64grams of monoisopropyl amine in 10 ml. of chloroform. Stirring at roomtemperature for 2 more hours, washing with dilute HCl, dilute NaHCO andwater, drying over anhydrous MgSO and high vacuum stripping gave 9.8grams (94% yield) of S- 2,2-dichlorovinyl methylthiophosphon-N-monoisopropyl amidate (Compound 7590) as an amber oil 121.5882; CI, 27.2% (theory, 26.8%); P, 11.4% (theory 11.7%); S, 23.3%(theory, 24.2%).

EXAMPLE 1 l 9.5 grams (0.037 mole) of CP 33 in 100 ml. of chloroform wasreacted with 4.4 grams of monoisopropyl amine (an excess )in 10 ml. ofchloroform by dropwise addition of the amine solution with stirring at510 C. with cooling. The mixture was warmed for 30 further minutes at45-50 C. Washing when cooled to room temperature with dilute HCl, dilueNaHCO and water, drying over MgSO and high vacuum stripping gave grams(97% yield) of S-2,2-dichlorovinyl ethyl thiophosphon- N-monoisopropylamidate (Compound 7592) as an amber oil, 11 15807.

EXAMPLE 12 To 12 grams (0.039 mole) of CP 11 in 100 ml. of carbontetrachloride there were added 3 grams (an excess) of ethyl mercaptanfollowed by dropwise addition with stirring and cooling of 4 grams (thecalculated amount) of triethylamine at 2530 C. Further stirring at roomtemperature overnight, washing with dilute HCl, dilute NaHCO and water,drying over MgSO and stripping gave 11 grams (85% yield) ofS-2,2-dichlorovinyl-S-ethyl-phenyl-thiophosphonate (Compound 7830) as alight yellow oil, 113 1.6634.

EXAMPLE 13 10 grams (0.382 mole) of CP 12 were diluted with 75 ml. ofbenzene and 2.5 grams (0.4 mole, slight excess) of ethyl mercaptan wereadded at room temperature followed by dropwise addition with stirring of3.9 grams (0.28 mole) of triethylamine at such a rate (occasionalcooling) that the temperature was continued for 2.5 hours and the wholewas allowed to stand overnight with stirring. Filtration, washing of theclear benzene solution with dilute HCl and dilute bicarbonate, dryingover magnesium sulfate and high vacuum stripping gave 9.5 grams (87%yield) of S-2,2,2-trichloroethyl-S-ethylmethylphosphonate as lightyellow oil, n1 1.5621.

EXAMPLE 14 10 grams (0.38 mole) of CP 12 were diluted with 75 ml. ofbenzene, 1.9 grams ethanol (0.4 mole, slight excess) added at once atroom temperature followed by dropwise addition with stirring of 3.9grams (0.38 mole) of triethylamine at a temperature not to exceed 25 C.Standing overnight at room temperature and washing as described inExample 13 followed by high vacuum stripping gave 9 grams (87% yield) ofS2,2,2-trichloroethyl-O-ethyl-methylphosphonate as reddish oil, n1.5148.

EXAMPLE 15 10.5 grams (0.4 mole) of CP 12 were diluted with ml. ofchloroform and reacted with a total of 4.8 grams (0.8 mole) ofisopropylamine by dropwise addition with stirring and cooling at atemperature of between 10 and 20 C. After completed addition of thereagent the mixture was allowed to stir for a further /2 hour at roomtemperature followed by standing overnight. After a brief warming periodto 50 C. next day (15 minutes) and cooling, the mixture was washed insuccession with water, dilute HCl and dilute bicarbonate, dried overanhydrous magesium sulfate and stripped in high vacuum. 11 grams (97%yield) of compound S-2,2, 2-trichloroethyl-methylphosphonmonoisopropylamidate were thus obtained as reddish oil, 11 1.5196.

EXAMPLE 16 8 grams (0.3 mole) of CP 12 were diluted with ml. of benzeneat room temperature and 7.1 grams (0.7 mole) dis-isopropylamine wereadded dropwise with stirring allowing the temperature to rise to 35 C.Stirring was continued at room temperature for approximately 3 hours andthe whole was allowed to stand overnight at room temperature. Thefollowing day the mixture was washed in succession with dilute HCl,dilute bicarbonate, dried over anhydrous magnesium sulfate, and highvacuumed stripped. 1.5 grams (12.8% yield) ofS-2,2,2-trichloroethyl-methylphosphon-N,N-di-isopropylamidate wereobtained as brownish oil, 11 1.5432.

EXAMPLE 17 10 grams (0.445 mole) of CP 14 were diluted with 100 ml. ofbenzene and 2.3 grams (0.5 mole) of dry ethyl alcohol added at roomtemperature. To this solution there were added slowly with stirring andoccasional cooling 4.5 grams (0.0445 mole) of triethylamine dropwisewith stirring at such a rate that the temperature did not exceed 25 C.After completed addition of the reagent, stirring was continued for afuther 2 /2 hours and the whole was allowed to stand overnight at roomtemperature. Washing the mixture'with dilute HCl, dilute bicarbonate,drying the solution over anhydrous magnesium sulfate and high vacuumstripping gave 9' grams (86% yield) ofS-2,2-dichlorovinyl-O-ethyl-methylphosphonate as amber oil.

EXAMPLE 18 13.55 grams (0.6 mole) of CP 14 were diluted with 100 ml. ofdry chloroform and 3.72 grams (slight excess) of ethyl mercaptan wereadded at room temperature at once. 6.06 grams (0.6 mole) oftriethylamine were then added dropwise with stirring and cooling at arate that the temperature remained below 25 C. Allowing the mixture tostand overnight, washing with dilute HCl, sodium bicarbonate, dryinganhydrous magnesium sulfate and high vacuum stripping gave 12.4 grams(83% 7 yield) of S-2,2-dichlorovinyl-S-ethyl-methylphosphonate as almostcolorless oil, 11 1.5616.

EXAMPLE 19 grams (0.445 mole) of CP 14 were diluted with 100 n11. ofbenzene and 10.1 grams (0.1 mole) of dilute isopropylamine were addeddropwise With stirring and cooling at such a rate as to keep thetemperature below 25 C. After completed addition, stirring was continuedat room temperature for 4 hours. After standing the mixture overnight atroom temperature, heating to 50 for 30 minutes was applied followed bycooling. The mixture was then washed as usual with dilute HCl andbicarbonate solution, dried over anhydrous magnesium sulfate and highvacuum stripped. 2 grams (15% yield) ofS-2,2-dichlorovinyl-methylphosphon N,N di-isopropylamidate were obtainedas red oil, 11 1.5590.

EXAMPLE 10 grams (0.036 mole) of CP 16 were diluted with 75 ml. of drybenzene and 1.48 grams (0.04 mole) of dry ethanol were added at roomtemperature. 3.64 grams of triethylamine (0.036 mole) were then addeddropwise with stirring and cooling at a temperature below C. Stirringwas then continued for 2 further hours at room temperature and the wholewas allowed to stand overnight. Washing the mixture with dilute HCl,dilute bicarbonate, drying over magnesium sulfate and high vacuumstripping gave 9 grams (87% yield) ofS-2,2,2-trichloroethyl-O-ethyl-methylthiophosphonate as yellowish oil, n1.5644.

EXAMPLE 21 10 grams (0.036 mole) of CP 16 were diluted with 75 ml. ofbenzene and 2.48 grams (0.04 mole) of ethyl mercaptan added at roomtemperature. 3.64 grams of triethylamine (0.036 mole) were then addedslowly with stirring and cooling at a temperature not to exceed 25 C.After the addition of the triethylamine, stirring was continued for afurther 2 hours and the mixture was allowed to stand overnight. Washingin order with dilute HCl, dilute bicarbonate, drying over magnesiumsulfate and high vacuum stripping gave 10.5 grams (97% yield) of S-2,2,2trichloroethyl S ethyl-methylthiophosphonate as yellow oil, n 1.6048.

EXAMPLE 22 10 grams (0.036 mole) of CP 16 were diluted with 100 ml. ofbenzene and 8.1 grams (0.08 mole) of diisopropylamine were added to themixture dropwise with stirring and cooling at a temperature between 20and 25 C. Stirring for an additional 4 hours at room temperature (25 C.)and standing overnight was applied followed by a 15 minute heatingperiod to 50 C. The cold mixture was then washed as usual with diluteHCl, bicarbonate and water, dried over anhydrous magnesium sulfate andvacuum stripped. 4.5 grams (87% yield) ofS-2,2,2-trichloroethyl-methylphosphon-N,N-di-isopropylamidate wereobtained as dark amber oil, n 1.6044.

EXAMPLE 23 8 grams (0.033 mole) of CP 16 were diluted with 100 ml. ofbenzene, 2 grams (0.04 mole) of ethanol added at room temperature andreacted by dropwise addition of 3.5 grams of triethylamine (0.033 mole)with stirring and cooling at a temperature not to exceed C. Additionalstirring at room temperature for 1.5 hours, washing of the resultingmixture with dilute HCl, bicarbonate and water, drying over magnesiumsulfate and vacuum stripping gave 8 grams ofS-2,2-dichlorovinyl-S-ethyl-methyl-thiophosphonate as amber oil.

EXAMPLE 24 7 grams (0.029 mole) of CP 15 were dissolved in 100 ml. ofchloroform and 2.5 grams ethyl mercaptan excess together with 10 ml. ofchloroform added at room temperature. 3.39 grams (0.03 mole) oftriethylamine and 10 ml. of chloroform were added dropwise with stirring8 and occasional cooling at a temperature not to exceed 25 C. Washingwith water, dilute HCl, dilute bicarbonate, drying of the chloroformsolution over anhydrous magnesium sulfate and stripping in high vacuumgave 7.5 grams (98% yield) ofS-2,2-dichlorovinyl-S-ethylmethyl-thiophosphonate as almost colorlessoil, 11 1.6312.

EXAMPLE 25 8.0 grams of CP 15 (0.033 mole) were dissolved in 150 ml. ofbenzene and reacted by adding 7.51 grams (0.07 mole) ofdi-isopropylamine dropwise with stirring and cooling. Stirring for anadditional 1.5 hours at room temperature was applied to complete thereaction. After washing this solution with dilute HCl, dilutebicarbonate and water, drying over anhydrous magnesium sulfate and highvacuum stripping, 5 grams of S-2,2-dichlorovinylmethylthiophosphon-N,N-diisopropylamidate were obtained as reddish oil.

EXAMPLE 26 To 6 grams (0.0226 mole) of CP 22 in 75 ml. of benzene therewere added at room temperature 1.4 grams (0.03 mole) of dry ethanol. 2.3grams (0.0226 mole) of triethylamine were then added with stirring andcooling dropwise at such a rate as to keep the temperature below 25 C.After completed addition, stirring for 1.5 hours at room temperature andstanding overnight, the mixture was washed in order with dilute HCl,dilute bicarbonate and water, dried over anhydrous magnesium sulfate andhigh vacuum stripped. 5 grams (78% yield) of S-2,2,2-trichloroethyl-O-ethyl-ethylphosphonate were obtained as yellow oil, n1.5085.

EXAMPLE 27 To 10 grams (0.036 mole) of CP 22 in 75 ml. of benzene 2.5grams (0.04 mole) of ethyl mercaptan were added at room temperature.3.66 grams (0.036 mole) of triethylamine were then added dropwise withstirring and cooling at a temperature below 25 C. After completedaddition of the reagents stirring was continued for 2% hours and theWhole was allowed to stand overnight. The mixture was washed as usualwith dilute HCl, dilute bicarbonate and water, dried over anhydrousmagnesium sulfate and high vacuum stripped. 10 grams (92% yield) ofS'2,2,2-trichloroethyl-S-ethyl-ethylphosphonate were obtained as yellowoil, In, 1.5565.

EXAMPLE 28 13.8 grams (0.05 mole) of CP 22 were dissolved in 150 ml. ofether and 10.1 grams di-isopropylamine (0.1 mole) were added slowlydropwise with stirring at room temperature. After completed addition ofthe reagent, stirring was continued at room temperature for oneadditional hour. The whole was washed with water, dried over magnesiumsulfate and high-vacuum-stripped. 1 gram ofS-2,2,2-trichloroethyl-ethylphosphon-N,N-di-isopropylamidate as aviscous oil was obtained. (Most of the compound was lost in the waterWash.)

EXAMPLE 29 To 10 grams (0.042% mole) of CP 23 dissolved in ml. ofbenzene, 2.3 grams (0.05 mole) of dry ethanol were added at roomtemperature. 4.22 grams (0.042 mole) of dry ethylamine were then addedslowly dropwise with stirring and occasional cooling at a temperaturenot to exceed 25 C. After completed addition of the reagent, stirringwas continued for 2 /2 hours and the whole was allowed to standovernight. Washing of the resulting mixture as usual with dilute HCl anddilute bicarbonate, drying over anyhdrous magnesium sulfate and vacuumstripping gave 9 grams (87% yield) ofS2,2-dichlorovinyl-O-ethyl-ethylphosphonate as red oil, n 1.5270.

EXAMPLE 30 10 grams (0.042 mole) of CP 23 were dissolved in 100 ml. ofpetroleum ether and 5 grams (slight excess over 2 molar proportion) in15 ml. of petroleum ether were added dropwise with stirring and coolingat a temperature below 10 C. (ice water bath). Stirring overnight,washing with water, dilute HCl, dilute bicarbonate, drying overmagnesium sulfate (50 cc. benzene were necessary to render mixturehomogeneous) and high vacuum stripping gave 9.5 grams (87% yield),S-2,2-dichlorovinylethylphosphon-N-isopropylamidate as a light viscousoil, 11 1.5460.

EXAMPLE 31 12 grams (0.05 mole) of CP 23 were dissolved in 100 ml. ofdry benzene and 11.1 grams (0.11 mole) of diisopropylamine were addedwith stirring dropwise at about 25 C. After completed addition of thereagents the mixture was stirred for 4 additional hours and finallyallowed to stand at room temperature overnight. Heating to 50 C. for 30minutes to complete the reaction and cooling followed by washing, dryingover anhydrous magnesium sulfate and high vacuum stripping, gave 1.5grams (10% yield) of S-2,2-dichlorovinyl-ethyl-phosphon-N,N-di-isopropylamidate as dark oil, n 1.5500.

EXAMPLE 32 To 7 grams of CP 32 (0.24 mole) diluted with 75 ml. ofbenzene 1.4 grams (0.3 mole) of dry ethyl alcohol were added at once atroom temperature. 2.5 grams (0.24 mole) of triethylamine diluted with 25ml. of dry benzene were then added dropwise with stirring and occasionalcooling at a temperature below 25 C. Standing overnight, washing of themixture with dilute HCl, dilute bicarbonate, drying over anhydrousmagnesium sulfate and high vacuum stripping gave grams (69% yield) ofS-2,2,2-trichloroethyl O ethyl-ethylphosphonate as a yellow oil, n1.5840.

EXAMPLE 33 grams (0.034 mole) of CP were diluted with 75 ml. of benzeneand 2.5 grams (0.04 mole) of ethyl mercaptan were added at roomtemperature. 3.5 grams (0.034 mole) of triethylamine diluted with 25 ml.of benzene then were added dropwise with stirring and occasional coolingat a temperature below 25 C. Stirring for an additional 3 hours,allowing to stand overnight, washing the resulting solution in orderwith dry HCl, bicarbonate and water, drying over anhydrous magnesiumsulfate and high vacuum stripping gave 10.5 grams (97% yield of S-2,2,2-trichloroethyl-S-ethyl-ethylthiophosphonate as a colorless oil, 111.5992.

EXAMPLE 34 14.6 grams (0.05 mole) of CP 32 were diluted with 150 ml. ofether and 10.1 grams of di-isopropylamine (0.1 mole) were added dropwisewith stirring and occasional cooling. The reaction is exothermic butprecipitation was poor. After completed addition, stirring was continuedfor one further hour. In order to complete the reaction (pH was stillbasic) the mixture was heated to slight reflux for 30 minutes. Cooling,filtration with charcoal, and high vacuum stripping of the ethersolution without washing gave 9 grams ofS-2,2,2-trichloroethyl-ethylthiophosphon-N,N-di-isopropylamidate asviscous oil, 50% yield.

EXAMPLE 35 To a solution of 13 grams (0.02 mole) of GP 33 in 100 ml. ofbenzene 3 grams (0.06 mole) of dry ethyl alcohol were added followed bySgrams (0.05 mole) of triethylamine which was added slowly with stirringat room temperature. The addition temperature was kept below 35 C. withoccasional cooling. After completed addition, stirring was continued fortwo more hours at room temperature, cooled, washed as usual with diluteHCl, dilute bicarbonate and water, dried over anhydrous magnesiumsulfate, filtered and high vacuum stripped. 10 grams (76% yield) ofS-2,2-dichlorovinyl-O-ethyl-ethylthiophosphonate were obtained as ayellow oil.

EXAMPLE 36 To 13 grams (0.05 mole) of CP 33 in 100 ml. of benzene, 3.1grams (0.05 mole) of ethyl mercaptan were added at room temperature. 5grams (0.05 mole) of triethylamine were then added dropwise withstirring at room temperature allowing the mixture to warm to 35 C. Aftercompleted addition, stirring was continued for two more hours at roomtemperature, cooled, washed as usual with dilute HCl, dilute bicarbonateand water, dried over anhydrous magnesium sulfate, filtered and highvacuum stripped. 10 grams (76% yield) ofS-2,2-dichlorovinyl-S-ethyl-thiophosphonate were obtained as yellow oil.

EXAMPLE 37 To a solution of 12.8 grams (0.05 mole) of CP 33 in 100 ml.of benzene 11.1 grams of di-isopropylamine (0.11 mole) were addeddropwise with stirring and cooling at 25 C. After completed addition ofthe reagent, stirring was continued for a further four hours. Allowingto stand overnight, heating to 50 C. for 30 minutes and coolingcompleted the reaction. The resulting mixture was then washed as usualwith dilute HCl, dilute bicarbonate and Water, dried over magnesiumsulfate and high vacuum stripped. grams (60% yield) ofS-2,2-dichlorovinylethylthiophosphon-N,N-isopropylamidate were obtainedas amber oil, n 1.5595.

EXAMPLE 38 9.72 grams (0.03 mole) of CP 8 were added dropwise withcooling to 60 ml. of dry ethyl alcoholthe large excess serving ass0lventfollowed by dropwise addition of 3 grams (0.03 mole) oftriethylamine with stirring and cooling at a temperature of below 35 C.After allowing the mixture to stir at room temperature for severalhours, the ethyl alcohol was evaporated in vacuum and the residue washedin water to remove most of the triethylamine hydrochloride. The formedoil was then taken up with Skellysolve B, washed twice with dilute HCland water, dried over magnesium sulfate and stripped in high vacuum. 10grams (quantitative yield) of S-2,2,2-trichloroethyl-O-ethyl-phenylphosphonate was obtained as a light yellowoil.

EXAMPLE 39 To a solution of 9.7 grams (0.03 mole) of CP 8 in 50 ml. ofdry benzene, 3.6 grams (0.06 mole) of monoisopropylamine were addeddropwise with stirring at room temperature wtih occasional cooling.After completed addition of the reagent, the mixture was stirred for afurther two hours at room temperature. The resulting mixture was washed,dried over magnesium sulfate and high vacuum stripped. 9.5 grams (92%yield) of S-2,2,2-trichloroeth'yl-phenylphosphon-mono-isopropylamidatewere obtained as a white solid, melting point 103117 C.

EXAMPLE 40 9.7 grams (0.03 mole) of CP 8 were diluted with 50 ml. ofbenzene and 6.1 grams (0.06 mole) of diisopropylamine were addeddropwise with stirring at room temperature. Additional stirring for twohours and standing overnight completed the reaction. Washing as usual,drying over magnesium sulfate and high vacuum stripping gave 5 grams(43% yield) of 8 2,2,2-trichloroethyl-phenylphosphon-diisopropylamidateas yellow oil, n 1.5445.

EXAMPLE 41 10 grams (0.035 mole) of CP 10 were dissolved in ml. ofbenzene and 2.12 grams (0.04 mole) of dry ethanol were added at roomtemperature. 4.04 grams (0.04 mole) of triethylamine were then addeddropwise with stirring and occasional cooling followed by an additionalstirring period of 2 /2 hours. Allowing to stand overnight, washing ofthe resulting mixture with dilute HCl, dilute bicarbonate and water,drying over anhydrous magnesium sulfate and high vacuum stirpping gave10 grams of 1 1 S-2,2-dichlorovinyl O ethyl-phenylphosphonate (97%yield) as red oil, 11 1.5702.

EXAMPLE 42 14.3 grams (0.05 mole) of CP were diluted with 100 ml. ofcarbon tetrachloride and 3.1 grams (0.05 mole) of ethyl mercaptan wereadded at room temperature (25 C.). 5.0 grams (0.05 mole) oftriethylamine were then added to the mixture dropwise with stirring andcooling. Additional stirring at room temperature for 48 hours completedthe reaction. Filtration, washing of the organic layer with dilute HCland water, drying over magnesium sulfate and high vacuum stripping gave14.5 grams (93% yield) of S-2,2-dichlorovinyl-S-ethyl-phenylphosphonateas yellow oil, n 1.6216.

EXAMPLE 43 14.3 grams (0.05 mole) of CP 10 were diluted with 75 m1. ofbenzene and 6 grams (0.1 mole) of monoisopropylamine added with stirringat room temperature with occasional cooling. Standing overnight wasapplied for completion of the reaction. Washing of the obtained mixture,drying over magnesium sulfate and stripping in vacuum gave 12.5 grams(81% yield) of S-2,2-dichlorovinylphenylphosphon-monoisopropylamidate asa white solid melting point 75-87.

EXAMPLE 44 10 grams (0.035 mole) of CP 10 were diluted with 100 m1. ofbenzene at room temperature and 4.04 grams (0.04 mole) ofdi-isopropylamine were added dropwise with stirring at between -25 C.(cooling by means of an icewater bath). Additional stirring for 2% hoursand standing overnight was applied to complete the reaction. The mixturewas then washed as usual, dried over magnesium sulfate and high vacuumstripped. 8.5 grams (70% yield) ofS-2,2-dichlorovinyl-phenylphosphon-di-isopropylamidate were obtained asviscous oil, r1 1.5626.

EXAMPLE 45 10.2 grams (0.03 mole) of CP 9 were dissolved in 50 ml. ofbenzene and 3 grams (0.03 mole) of ethyl mercaptan were added at roomtemperature. To this mixture, 3 grams (0.03 mole) of triethylamine wereadded dropwise with stirring and occasional cooling at a temperature notto exceed 25 C. After allowing to stir the mixture for an additional 2hours, washing of the resulting mixture as usual, drying over magnesiumsulfate and high vacuum stripping, 11 grams (quantitative yield)S-2,2,2- trichloroethyl S ethyl-phenylthiophosphonate were obtained ascolorless oil, 11 1.6320.

EXAMPLE 46 10.2 grams (0.03 mole) of CP 9 were dissolved in 50 ml. ofbenzene and 3.6 grams (0.03 mole) of monoisopropylamine were addeddropwise with stirring and cooling at between 25 and C. Stirring wasthen continued for another two hours at room temperature and the wholewas allowed to stand overnight. The resulting mixture was washed asusual with dilute HCl, dilute bicarbonate and water, dried overanhydrous magnesium sulfate and high vacuum stirpped. 9 grams (83%yield) of S-2,2,2-trichloroethyl-phenylthiophosphon-mono-isopropylamidate were obtained as a colorless oil, 11 1.6666.

EXAMPLE 47 10.2 grams of CP 9 (0.03 mole) were diluted with 50 ml. ofdry benzene and 6.1 grams (0.06 mole) of di-isopropylamine were addeddropwise with stirring and cooling at room temperature. Allowing to stirfor a further two hours at room temperature and standing overnightcompleted the reaction. Washing with dilute HCl, dilute bicarbontae andwater of the resulting mixture, drying over magnesium sulfate and highvacuum stripping gave 7 grams (59% yield) ofS-2,2,2-trichloroethyl-phenylthio- 12 phosphon-di-isopropylamidate as anofli-white solid, melt ing point 92-100 C.

EXAMPLE 48 10 grams (0.033 mole) of CP 11 dissolved in 100 ml. ofbenzene were mixed with 2.12 grams of dry ethanol (0.04 mole) of 4.04grams (0.04 mole) of triethylamine were added to this mixture dropwisewith stirring and occasional cooling at room temperature. Aftercompleted addition of the reagents, stirring was continued for a furthertwo hours at room temperature. After allowing the resulting mixture tostand overnight it was washed in succession with dilute HCl, dilutebicarbonate and water; drying over anhydrous magnesium sulfate and highvacuum stripping gave 10.5 grams (quanititative yield) ofS-2,2-dichlorovinyl-0-ethyl-phenyl-thiophosphonate as a red oil, n1.5900.

EXAMPLE 49 12 grams (0.039 mole) of CP 11 were dissolved in 75 ml. ofbenzene and 4.7 grams (0.08 mole) of monoisopropylamine were addeddropwise with stirring and cooling at room temperature. After completedaddition of the reagent, the mixture was allowed to stand overnight.Washing, drying over magnesium sulfate and high vacuum stripping gave10.5 grams (81% yield) of S-2,2- dichlorovinyl-phenyl-thiophosphon-monoisopropylamidate as amber oil, n 1.6246.

EXAMPLE 50 10 grams (0.033 mole) of CP 11 diluted with 100 ml. ofbenzene and a mixture of 4.04 grams (0.04 mole) of di-isopropylamine and4.04 grams tri-ethylamine (0.04 mole) in 25 ml. of benzene is addeddropwise with stirring and cooling at 20-25 C. Additional stirring for 2hours and allowing to stand overnight gave after filtration, washing(dilute HCl, NaHCO drying (MgSO and high vacuum stripping 8 grams (66%yield) of S-2,2- dichlorovinyl-phenyl-thiophosphon-di-isopropylamidateas a viscous oil, n 1.6400.

EXAMPLE 5 1 3.0 grams (0.062 M, excess) of methyl mercapto gas Wereintroduced at 70 C. into a solution of 8.7 grams (0.033 M) of CP 12 in60 ml. of dry Skellysolve B and 40 ml. of benzene. Then, with ice watercooling, 3.4 grams (0.033 M, slight excess) of Et N in 10 ml. of SkellyB were added dropwise with stirring at 1520 C. After a two hour standingperiod at room temperature, the mixture was washed (water, dilute HCl,dilute NaHCO dried (over MgSO and stripped in vacuum (.05 mm. Hg, 50C.), 7.5 grams (84% yield) of S-2,2,2- trichloroethyl-S-rnethyl-methylphosphonate were obtained as almost colorless oil, which solidified onprolonged standing.

EXAMPLE 52 7.5 grams (0.0285 M) of CP 12 were dissolved in 70 ml. ofSkellysolve B, 4 grams (0.045 M, large excess) of BuSH added withice-water cooling and 2.9 grams (0.0285 M) of Et N in 10 ml. ofSkellysolve B added at 1520 dropwise with stirring and cooling. Stirringfor a further 30 minutes at room temperature, washing (H dilute HCl,dilute NaHCO drying (MgSO and stripping (.05 mm. Hg, 70 C.) gave 7.5grams (85% yield) of S-2,2,2-trichloroethyl-S-butyl-methyl phosphonateas pale yellow liquid.

EXAMPLE 53 7.6 grams (0.029 M) of CP 12 were dissolved in 50 ml. of 1:1Skellysolve B-benzene and 6.2 grams (0.058 M) of N-methyl aniline in 20ml. of benzene added. The reaction proceeded at a reasonable rate atslightly elevated temperatures. When all the aniline was added a twohours heating period at 550 C. was sufiicient to complete the reaction.Cooling to room temperature and 13 filtration, followed by washing(dilute HCl, NaHCO and water), drying (MgSO and vacuum stripping gave 8grams (85% yield) of S-2,2,2-trichloroethyl-methylphosphon-N,N-methyl-phenyl amidate as a light brown oilwhich solidified on prolonged standing.

EXAMPLE 54 2.2 grams (0.025 M) of piperazine and 5.1 grams (0.05 M) ofEt N were dissolved together in 100 ml. of CHCIg. 13.8 grams (0.05 M) ofCP 22 (S-2,2,2-trichloroethyl ethyl thiophosphonyl chloride) were thenslowly added dropwise with stirring at 20-25" C. and occasional cooling.Two hours continuous stirring at room temperature, washing (water,dilute HCl, dilute HCl, dilute NaHCO drying (MgSO' and stripping gave11.5 g. (80%) of bis[S-2,2,2 trichloroethyl-ethyl-thiophosphonyl]piperazine-1,4 as crude dark oil, which solidified. Washing with freshbenzene gave a buff colored solid, m. 160-8 C.; percent Cl, 37.7 calc.,36.5 fd.; percent P, 11.0 calc., 10.9 fd.

EXAMPLE 55 8 grams (0.025 M) of CP 8 were dissolved in 150 ml. of drypetroleum ether and a total of 3 grams (0.067 M, excess) of dimethylamine gas was introduced at a temperature below 10 C. with stirring andcooling over a period of approximately minutes. Prolonged stirring for30 minutes at below 15 C. and at room temperature for a further twohours, removing of the formed dimethylamine hydrochloride by washing(water, dilute HCl, dilute NaHCO drying and stirring in vacuum gave 8.2grams (quantitative yield) ofS-2,2,Z-trichloroethyl-phenyl-phosphon-N,N-dimethyl-amidate as a lightyellow, mobile liquid, n 1.5790; percent Cl, 31.9 calc., 32.5 fd.;percent P, 9.3 calc., 9.7 fd.; and percent N, 4.2 calc., 3.9 fd.

EXAMPLE 56 9.72 grams (0.03 M) CP 8 were dissolved in 75 ml. petroleumether and 25 ml. of benzene 4.24 grams (0.029 M) of p-chloro thiophenoladded at room temperature followed by dropwise addition with stirringand cooling of 3 grams (0.3 M) of Et N at below 35 C. followed in turnby heating for minutes at 55 C. and allowing to cool to room temperaturewith stirring. Washing (water, dilute HCl, dilute NaHCO drying over anh.MgSO and stripping in high vacuum gave 11.5 grams (89% yield) ofS-2,2,2-trichloroethyl-S-p-chlorophenylphenyl-phosphonate as a veryheavy oil, 11 1.6415; percent Cl, 32.9 calc., 33.2 fd.; percent P, 7.2calc., 6.8 fd.

EXAMPLE 57 9.72 grams (0.03 M) of CP 8 were dissolved in a mixture of 75ml. petroleum ether and 25 ml. benzene, 3.8 grams (0.03 M) ofp-chlorophenol added followed by dropwise addition with stirring andcooling at below C. of 3 grams (0.03 M) of Et N. A short period ofheating to 55 C. and allowing to cool to room temperature over a totalperiod of one hour was applied to assure quantitative reaction. Washing(water, dilute HCl, dilute NaCHO drying (MgSO and stripping (vacuum)gave 11.0 grams (88% yield) ofS-2,2,2-trichloroethyl-O-pchlorophenyl-phenyl-phosphonate, percent Cl,34.2 calc., 33 fd.; percent P, 7.5 fd.

EXAMPLE 5 8 9.72 grams (0.03 M) of CP 8 were dissolved in 150 ml. ofbenzene 4.3 grams (0.031 M) of Et N. Heating for a short period of timeto 55 C., allowing to stir at room temperature overnight, washing(water, dilute HCl, dilute NaHCO drying (MgSO and stripping (vacuum)gave a total of 11.5 grams (90% yield) of crudeS-2,2,2-trichloroethyl-O-p-nitrophenyl phenyl phosphonate, which onrecrystallizing gave m. 93-6 C. Percent Cl, 24.9 calc., 24.9 fd.;percent P, 7.3 calc., 7.5 fd.; percent N, 3.3 calc., 3.2 fd. (IR 57).

The pesticides of the present invention can be used alone or they can beapplied together with inert solids to form dusts, or can be suspended ina suitable liquid dilute, e.g. organic solvents or water.

There can also be added surface active agents or wetting agents and/orinert solids in the liquid formulations. In such case, the activeingredient can be from 0.01 to by weight of the entire composition.

As organic solvents there can be employed hydrocarbons, e.g. benzene,toluene, xylene, kerosene, diesel fuel, fuel oil, and petroleum naphtha,ketones such as acetone, methyl ethyl ketone and cyclohexanone,chlorinated hydrocarbons such as carbon tetrachloride, chloroform,trichloroethylene, and perchloroethylene, esters such as ethyl acetate,amyl acetate and butyl acetate, ethers, e.g. ethylene glycol monomethylether and diethylene glycol monomethyl ether, alcohols, e.g. methanol,ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol,butyl carbitol acetate and glycerine. Mixtures of water and organicsolvents, either as solutions or emulsions, can be employed.

The novel pesticides can also be applied as aerosols, e.g. by dispersingthem in air by means of a compressed gas such as dichlorodifiuoromethaneor trichlorofiuoromethane and other Freons and Genetrons, for example.

The pesticides of the present invention can also be applied withadjuvants or carriers such as talc, pyrophyllite, synthetic fine silica,attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calciumcarbonate, bentonite, fullers earth, cotton-seed hulls, wheat flour,soybean flour, pumice, tripoli, wood flour, walnut shell flour, redwoodflour and lignin.

As stated, it is frequently desirable to incorporate a surface agentagent in the pesticidal compositions of the present invention. Suchsurface active or wetting agents are advantageously employed in both thesolid and liquid compositions. The surface active agent can be anionic,cationic or nonionic in character.

Typical classes of surface active agents include alkyl sulfonate salts,alkylaryl sulfonate salts, alkylaryl polyether alcohols, fatty acidesters of polyhydric alcohols and the alkylene oxide addition productsof such esters, and addition products of long chain mercaptans andalkylene oxides. Typical examples of such surface active agents includethe sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in thealkyl group, alkylphenol ethylene oxide condensation products, e.g.p-isooctylphenol condensed with 10 ethylene oxide units, soaps, e.g.sodium stearate and potassium oleate, sodium salt of propylnaphthalenesulfonic acid, di (2-ethylhexyl) ester of sodium sulfosuccinic acid,sodium lauryl sulfate, sodium decane sulfonate, sodium salt of thesulfonated monoglyceride of coconut fatty acids, sorbitan sesquioleate,lauryl trimethyl ammonium chloride, octadecyl trimethyl ammoniumchloride, polyethylene glycol lauryl ether,

polyethylene glycol esters of fatty acids and rosin acids,

e.g. Ethofat 7 and 13, sodium N-methyl-N-oleyl taurate, Turkey red oil,sodium dibutyl naphthalene sulfonate, sodium lignin sulfonate,polyethylene glycol stearate, sodium dodecylbenzene sulfonate, tertiarydodecyl polyethylene glycol thioether (Nonionic 218), long chainethylene oxide-propylene oxide condensation products, e.g. Pluronic 61(molecular weight 1000), polyethylene glycol ester of tall oil acids,sodium octyl phenoxyethoxyethyl sulfate, tris (polyoxyethylene) sorbitanmonostearate (Tween 60), and sodium dihexyl sulfo-succinate.

The solid and liquid formulations can be prepared by any of theconventional procedures. The compounds of the present invention can beapplied to soil, growing plants, e.g. trees, cotton plants, wheat andother grain plants, vegetable plants, seeds, fabrics, etc. to givepesticidal protection.

The compound can be used as nematocides at a dosage of 0.1 to lbs/acre,more usually from 1 to 30 lbs./ acre. As soil fungicides they areusually employed at a Vert.

16 F. ox. lyco for Fusarium oxy lycopersici icicles, they F. m'v. for Fusarium nivale Hel. sat. for Helminthosporz'um sativum Rhyz. sol. forRhizoctonia solani dextrose agar Vert. for Verticillium albo-atrum'! 2.the zulmredmedmm' In Table 1 the followmg abbrevl' The tests werecarried out at rates of 500 p.p.m., 100 a Ions e use p.p.m. and 10p.p.m. as shown in Table 1. In the table, 10 indicates 100%effectiveness (complete inhibition) and 0 indicates no effectiveness.

TABLE I.AGAR PLATES [Organism at p.p.m.]

C. U. Col. 0b. F. or. lyco F. m'v. Hel. sat. Rhyz. sol.

0 lbs./ acre. invention were tested foliar fungicides. As insect dosageof 0.5 to lbs/acre and as They are used at 0.1 to 20 lbs./ acre arenormally used in a dosage of 0.2 to 1 The compounds of the present asfungicides in agar plate tests using potato C.U. for Ceratacystis ulmiCol. 0b. for Colletorz'chium obiculare Structure 00 0 oomo 0000 50505580 oomo oomo oomo 0000 0050 0080 S Et NHiPro NiPlOg OEt SEt Me S CClz=CH SP NHiPro NiPrOn 0000 5550 mfim u 0000 OEt Et NHiPrO NiProz Et 0C ClaCHaS-P NHiPro NiProz s cousins-P NHiPro Ni P:

0000 005m 0025 0058 m m 0000 0000 0050 88880 sssm 00000 11111 50000 andstored at 40 F. for 5 days and then at 75 F. for 4 10 days. The canswere then removed and the rate of fungus growth recorded, with 10indicating no growth (perfect 18 control) and 0 indicating completegrowth (no control). The results are set forth in Table 2.

Some of the compounds were also tested in spore germination testsagainst Stemphylium sarcinaeforme and Ustilago kolleri spores. Thespores were dusted on agar containing the test compound dispersedtherethrough. The inoculated samples were incubated at room temperaturefor 24 hours and the germination recorded on a 0 to 10 scale with 10indicating no germination and 0 indicating germination. The results areset forth in Table 2 at the indicated dosages in ppm. The compounds wereless effective in this test than in the agar plate and soil fungicidetests.

TABLE 2.AGAR PLATES Soil fungicide rolled towel, lb a. Pythiurn Sporegerm.

Example Structure 200 50 500 100 10 13 Me O OEt SE1: CClaCHzS-P NHiProNiPlOz 0012=OHS-P NHiPro NiProz Ma S OEt;

SEt CClaCHzS-P NHiPrO NiProa Me S OEt 4 SEt 7 0 C12=CHSP NHiPro 4 NiProz1 Et 0 OEt 10 SEt 10 0 C]3OHzSP NHiPro 8 NiProz 5 Et 0 0E; 0 SE; 2CCIFCHS-P NI-IiPro 2 NiProz 7 Et; S DE; 0 SE1: 0 CCIaCHzS-P NHJ'Pro 5NiPlOz 0 Et S OEt 5 SE; 3 C C12=CHSP NHiPro 0 NiPrOn 7 Ph OEt; 0 0 0 0 0I SE1; 7 0 O 0 0 CClzCHzS P=O NHiPro 1 0 0 0 0 l NiPrOz 0 (l 5 0 0 Ph01% 3 2 5 0 0 SEt o o 5 0 0 CClz=CHSP=O NHiPro 2 2 10 0 0 l Nilroz 5 0Ph OEt 0 (l 10 5 0 I SEt; 0 0 0 0 0 001301128 P=S NHiPro 0 0 0 0 0 lNiProz 0 0 0 0 0 Ph OEt 2 3 SE; 0 0 5 0 0 CG1=CHS P=S NHiPro 4 4 0 0 0NiProz 1 Additional compounds 51 00130H2S(CH3)P(0)S0H3 52.. 0O130H2S(CH3)P(O)-S (CHMOH; 1... 001301123(0H3)P(O)-O(2,4C12)C5H 53CCISCHZS(CH3)P(O)-N(OH3)C8H5 [CClaCH2S(C2H5)P(S)]2N N 55 (C13CH2S(CaH5)P(O)-N(CH3)2 0 56 C C13CH2S (CsHs) P(O S (401) CeH4 5 57 001301128(C5H5)P(O)-O (401)09114 0 58. CC1aCHzS(CaH5 (O)O(4N0z) CaH 1 9CO12=CHS(CsH5)P(0)-N(CH3)2 3 The compounds were also tested asnematocides against both saprophytic and parasitic nematodes at therates of test compound in parts per million (p.p.rn.) set forth in Table3. In the saprophytic nematode test (NESA) water was used as the mediumwith Panagrellus spp. and

plants were transplanted into the soil and allowed to grow. The rootknots which formed on the roots of the plant were then measuredaccording to a root known index based on a -10 scale where 10 indicatescomplete absence of visible knotting and 0 indicates all roots wereRhabditis spp. The formulation employed included 50% heavily infested(knotted). Tomato plants transplanted to of the compound being tested,46% silica, 2% sodium the infested soil which did not contain thenematocide lignin sulfonate and 2% Pluronic L-61 (polyethylene had anaverage root knot index of 0 while tomato plants oxide-propylene oxideadduct moleculer weight about transplanted to soil which had beensteamed to kill all 1000). This formulation is formulation A. Theresults nematodes had an average root knot index of 10. The are given ona 0 to 10 scale with 10 indicating 100% term Pb in Table 3 indicatesphytotoxicity. As can be kill and 0 indicating no kill after a 4-dayincubation seen from Table 3 some of the compounds most effectiveperiod. against saprophytic nematodes had a considerably lesser In theparasitic nematode test (NEPA) the procedure eifect against parasiticnematodes and vice versa. This is was to add the test chemical informulation A to soil in accordance with the known fact that nematocideheavily infested with Meloidogyne spp. Then tomato activity is notpredictable.

TABLE 3 NESA NEPA Example Structure 400 200 25 200 12.5 6 3 13 Me 0 GE;10 8 SEt 10 10 {NHiPro 8 5 NiProz 1 1 OEt 5 0 {8151; 10 10 NHiPro 10 10NiProz 10 10 0131: 5 0 SEt 0 0 {NHiPro 5 3 NiPrOz 1 1 OEt 5 0 SEt 1 1{NHiPro 10 10 NiPro- 5 1 0E1; SEt {NHiPro NlPrOz OEt SEt {NHiPro NiProzOEt SEt {NHiPro NiPrOz OEt SEt {NHiPro NiPlOz Ph 0 OEt 8 8 3 0 SE1; 5 11 0 CChCHzSP NHiPro 5 a 3 9 NiProz 10 8 5 9 Ph 0 OEt 10 8 8 (Ph) SE1; 105 5 0 001 :0115? NHiPro 10 s a NiPIOl 10 8 0 (P11) P11 s 0131; 3 1 1 oSE1: 1 1 1 0 CChCHzS P NHiPro 1 1 1 o NiProz 1o 10 a 0 t 2 2 2 2 8 0 OCh=CHS P {NHiPro 5 1 1 0 NiProz 0 0 0 0 Additional compounds 200 OCl CHS(CH )P(O)-SCH3 3 1 1 o a 2 (CHa)P(O)S(CHzhCHa 5 1 1 0 CC1 CH S(CH)P(O)O(2.4C12)C5Ha .5 1 1 0 CCI3CHZS(CH3)P(O)N(CH3)C0H5 5 1 1 0 54[CCl3CHzS(CzH5)P(S)]zN N 3 1 1 55 (01301128(O6H5)P(O)-N(CH3)2 8 5 1 0CC13CH2S(O5H5)P(0)--S(4C1)C5H4 1 1 1 0 OCl CHzS(C@H )P(O)-O(4C1)CH4 3 11 0 CCI3CH2S(CBH5)P(O)O(4NO2)CBH4 1 1 1 0 9 CClz=CHS(CqH5)P(O)-N(CH3)1 85 5 0 The compounds were tested as pre-emergent and postemergentherbicides at the indicated dosages in lbs/acre. The results are setforth in Table 4. In the pre-emergent tests the readings are on a O-lOscale where is no effect and is complete inhibition of seeds togerminate and emerge. The compounds were applied in acetone solu- 5TABLE 4.-PRIM ARY HERBICIDE [Plants at 1b. 1 a.]

Japanese Pig weed Wild mustard Morning glory millet Water grass Wildoats Pre Post Pre Post Pre Post Pre Post Pre Post Pre Post EX. Structure5 8 2 15 5 8 2 15 5 8 2 15 5 8 2 15 5 8 2 15 5 8 2 13 Me O OEt 2 0 7 2 66 4 0 2 5 6 0 4 3 0 1 3 0 2 14 SEt 0 0 5 3 9 7 4 3 2 0 7 5 1 0 3 3 1 0 43 0 0 3 1 15. C Cl3CH2SP NHiPro 2 0 6 1 9 8 5 3 1 7 3 0 0 5 2 0 0 2 0 116. NiIIOg 17 Me\ //0 OEt 5 0 9 2 7 0 6 4 3 0 9 5 3 0 6 4 3 0 6 3 0 0 54 C CI =CH S -P\ Sugar beets 18 SE1; 0 0 9 8 (l 0 9 3 3 0 7 5 7 9 8 4 00 9 3 7 N HiPro 4 2 9 3 3 3 6 2 0 0 5 4 5 2 3 3 0 0 3 0 19 NiProz Wildoats Me S OEt 0 0 6 3 6 4 2 0 0 5 0 0 0 0 0 0 0 0 SEt 3 0 0 0 5 0 2 1 30 5 2 2 0 5 1 2 0 4 l 2 0 1 0 CCl3CHzSP NHiPrO 6 3 1 1 10 1 l 0 3 1 4 02 5 0 3 0 NiPrOz 23 Me\ S OEt 0 1 6 1 7 0 4 3 0 0 6 4 0 O 3 1 0 0 4 2 30 1 1 C Cl2=CH S P\ Sugar beets 24 SE1: 5 4 6 1 3 3 3 2 3 3 6 2 8 7 4 23 0 7 0 10 NHiPro 7 3 10 3 3 3 6 3 0 0 9 6 0 0 6 4 0 0 9 2 25 NiPro 2Et. Wild oats Et 0 OEt SEt 3 0 7 6 8 0 6 3 0 0 8 5 0 0 5 4 0 0 6 3 0 0 52 CClzOHzS-P NHiPro 3 2 4 3 9 9 3 1 2 0 4 1 0 0 4 2 1 0 5 3 1 0 1 1NiProz Et\ //0 OEt 3 3 9 5 7 6 6 4 3 4 8 8 3 4 5 3 3 4 6 4 0 0 6 3 C CICH S P Sugar beets SE1; 0 0 10 10 0 0 10 10 0 0 5 5 5 0 7 5 0 0 10 1ONHiPro 0 0 10 9 0 0 6 6 0 0 7 5 0 0 5 5 0 0 10 5 NiProa Wild oats Et SOEt 8 7 0 1 7 8 2 3 1 0 3 2 0 0 1 2 0 0 0 2 0 0 0 0 SE1: 6 0 3 1 1 1 4 31 1 3 1 4 0 4 0 6 0 4 0 2 0 3 0 CClaCHzS-P NHiPro 2 0 2 0 8 5 2 1 1 0 41 2 O 3 2 2 0 4 3 3 0 2 1 NiPrOz 0 0 7 7 0 0 6 6 0 1 7 7 0 0 4 3 0 O 6 30 2 1 1 Et S OEt 0 0 6 3 6 6 5 4 5 1 7 7 0 0 3 2 0 0 4 4 5 6 4 1 SE1: 72 3 1 3 2 5 3 5 3 4 4 4 3 2 2 3 3 3 2 5 6 0 0 C C12=CH S P NHiPlo 7 4 54 6 0 3 2 1 0 5 4 8 0 5 4 9 0 6 5 1 0 5 1 NiPIOz 0 0 6 1 0 0 6 3 0 0 8 50 0 5 2 0 0 6 2 0 0 4 0 Ph Sugar beets Radish Flax Wheat 38 Ph 0 DE: 0 09 3 O 0 8 4 0 0 6 3 0 0 6 2 3 3 6 1 SEt 0 0 8 3 0 0 7 3 0 0 4 2 0 0 3 10 0 3 C 0130 H: S P

\ Pig weed Wild mustard Morning glory Japanese millet 39 NHiPro 0 0 0 00 0 1 1 3 0 1 1 1 0 0 0 1 0 0 0 0 0 0 40 NiPro,

Ph 0 0121; 0 0 8 3 .0 0 7 3 0 0 9 4 0 0 7 3 0 0 6 3 0 0 1 0 SE1; 0 0 3 00 0 2 1 0 0 4 3 0 0 4 2 0 0 4 3 0 0 0 0 CC1z=CHSP NHiPlO 0 0 3 0 0 0 2 00 0 4 1 0 0 2 1 0 0 2 2 0 0 1 1 NiProa 0 0 3 0 0 0 3 4 0 O 5 3 0 0 4 0 00 3 0 D 0 0 0 Ph S OEt 0 0 0 0 0 0 2 2 0 0 1 2 0 0 0 0 0 0 0 0 0 0 0 0SE1; 0 0 4 3 0 0 3 1 0 0 5 3 0 0 3 3 0 0 3 2 O 0 0 0 C ClaCHa S P NHiPro0 0 0 0 0 0 2 2 0 0 1 2 0 0 0 0 0 0 0 0 0 0 0 0 NiPro; 0 0 1 0 0 0 1 1 00 1 2 0 0 0 0 0 0 1 0 0 0 0 0 Ph S 0131; 6 0 3 2 0 0 4 2 0 0 5 1 0 0 4 10 0 4 1 0 0 3 0 SE1; 0 0 2 1 0 0 2 1 0 0 4 3 0 0 4 3 0 0 6 3 0 0 1 0CCIz=CHS P NHiPro 1 0 2 1 0 0 1 1 1 0 2 1 0 0 2 1 0 0 4 3 0 0 4 1 NiProz2 0 5 3 9 0 4 4 3 0 6 3 0 0 3 2 0 0 4 2 0 0 1 0 TABLE6.-1NSECTICIDES-Continued [Rates at mmg/dish] Flour beetles House fly 2hrs. 18 hrs. 2 hrs 18 hrs.

Example Structure 1,000 100 10 1,000 100 10 1,000 100 10 1,000 100 10 54[CC13CH3S(C1H5)P(S)]3N N 55 (ChCHzS(CuH5)P(O)-N(CH5)1 so 0 0 0 0 0 0 025 0 CC13CHzS(C0H5)P(O)-S(4CDC0H4 0 0 0 0 0 0 0 5 0 0CCI3CH2S(COH5)P(O)'O(4CDCuH4 50 0 0 50 0 0 0 0 0 0 0 0CCI3CH2S(COH5)P(O)-O(4NO2)C6H4 0 o 0 0 0 0 0 0 0 0 CC1n=CHS(CeH)P(O)N(CH 0 0 0 o 0 0 0 5 0 0 The general observations from the testsare that the X areas of activity of the series of compounds tested ap- Rt! R pears to be in the order nematocidal, insecticidal and 1 fungicidalin the given order of priority. R:

The compounds where R is lower alkyl, e.g. methyl or ethyl appear to besuperior pesticides to those where R is phenyl.

The compounds having a P=S linkage on the whole appear to be betterpesticides than the compounds having a P=O linkage.

In the tests reported in the tables, the most useful compounds were2,2-dichlorovinyl-S-ethyl methyl thiophosphonate (nematocide and to alesser extent soil fungicide); S-2,2,2-trichloroethyl ethyl phosphonmonoisopropyl amidate (soil fungicide and to a lesser extent saprophyticnematocide); S-2,2,2-trichloroethyl-O-ethyl methyl thiophosphonate(nematocide); S-2,2,2-trichloroethyl-S-ethyl methyl thiophosphonate(nematocide); S- 2,2,2-trichlorocthyl-S-ethyl ethyl thiophosphonate(nematocide); S-2,2,2-trichloroethyl methyl thiophosphon monoisopropylamidate (insecticide); S-2,2,2-trichlor0- ethyl thiophosphonmonoisopropyl amidate (insecticide and to a lesser extent saprophyticnematocide); S-2,2-dichlorovinyl-ethyl thiophosphon monoisopropylamidate (insecticide and to a lesser extent parasitic nematocide andplate fungicide); and S-2,2-dichlorovinyl ethyl thiophosphonmonoisopropyl amidate (soil fungicide).

What is claimed is:

1. A method of killing nematodes comprising applying to the nematodes anematocidally effective amount of a compound having the formula where Ris trichloroethyl or dichlorovinyl, R is lower alkyl or phenyl, R is SRwhere R; is lower alkyl, phenyl, butylphenyl, chlorophenyl or methylchlorophenyl and X is O or S.

2. The method according to claim 1 wherein R is 2,2,2-trichloroethyl.

3. The method according to claim 1 wherein R is 2,2- dichlorovinyl.

4. The method according to claim 1 wherein R is lower alkyl.

5. The method according to claim 4 wherein X is O.

6. The method according to claim 4 wherein X is S.

7. The method according to claim 6 wherein R has 1 to 2 carbon atoms andR; has 1 to 4 carbon atoms.

References Cited UNITED STATES PATENTS 6/1963 Loeffier 4242l2 9/1965Schrader 424222 X US. Cl. X.R. 424222

